CN1901988A - Multi-tubular reactors with monolithic catalysts - Google Patents
Multi-tubular reactors with monolithic catalysts Download PDFInfo
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- CN1901988A CN1901988A CN200480039130.0A CN200480039130A CN1901988A CN 1901988 A CN1901988 A CN 1901988A CN 200480039130 A CN200480039130 A CN 200480039130A CN 1901988 A CN1901988 A CN 1901988A
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2485—Monolithic reactors
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00769—Details of feeding or discharging
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
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- B01J2219/2441—Other constructional details
- B01J2219/2443—Assembling means of monolith modules
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49345—Catalytic device making
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
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- Y10T29/4984—Retaining clearance for motion between assembled parts
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Abstract
Multi-tubular reactors for fluid processing incorporate reactor tubes containing thermally conductive monolithic catalyst structures with relative dimensions and thermal expansion characteristics effective to establish both a non-interfering or slidably interfering fit between the monolith structures and the reactor tubes at selected monolith mounting temperatures, and geometries at reactor operating temperatures such that the operating gaps between tubes and monoliths under the conditions of reactor operation do not exceed about 250 m over tube sections where high heat flux to or from the monoliths is required.
Description
Background of invention
The present invention relates to the application of monolithic catalyst in the multitube catalytic reactor.More specifically, the present invention relates to monolithic catalyst insert, fixing and remain on and be used in the pipeline of this reactor that chemical industry and/or energy transform industry or catalyst-assembly and method in shell-pipe in pipe.
At present, the tubular type catalytic reactor is used for various explained hereafter chemical reagent industrial.In reactor, the reaction logistics flow through have graininess, the pipeline of ring-type, catalyst bed such as spherical.These technologies comprise the technology that relates to the high heat release or the endothermic reaction, in order to carry out technology controlling and process, require reaction heat is handled.The example of high exothermic reaction comprises the selective catalytic oxidation organic compound, for example, benzene or n butane oxidation are become maleic anhydride, with the ortho-xylene oxidation to phthalic anhydride, methanol oxidation is become formaldehyde, makethe oxidation of ethylene to oxirane and Fischer-Tropsch synthetic method.The high endothermic reaction comprises that with hydrocarbon vapor reforming be synthesis gas (CO and H
2).For all these reactions, effectively the technological parameter that thermal control can the appreciable impact key comprises the selectivity of catalyst efficiency, reaction, enough catalyst service life, even the reactor security.
Tubular reactor is efficient relatively, but is difficult to control.For example " focus " can occur in exothermic reaction, this is unfavorable to reactor performance.Because for example the channel effect in the process flow and the very low fact of effective thermal conductivity of reaction system (catalyst granules adds gaseous reactant), the local heat that improves exothermic reaction speed can cause heat out of control.Under not controlled state, these reactions finally can cause sintering of catalyst or thawing, damage the shell of metallic reactors, even cause the reactor blast.The approach of handling these problems comprises Processing Strategies, as with catalyst segments, and perhaps diluting reaction thing; The latter is by as the circulation of response regulator, product or use the mode of inert diluent to carry out, but these strategies have reduced process efficiency inevitably.
Multi-tubular reactor provides a kind of high-efficiency method more of guaranteeing to control reaction zone temperature.These reactors generally include many pipelines, and its diameter is Centimeter Level normally, and the closs packing beaded catalyst is housed.The scope of reaction zone temperature control can enlarge by volume, flow or the thermal capacitance that reduces the tubular reactor diameter and/or improve various heat-exchange fluids (as already used gas, water, conduction oil and fuse salt).And, in the pellet type catalyst bed, can make the minimum or elimination of these channel effects that cause thermal runaway by replace ducted pellet type catalyst with encapsulating structure (for example, monolithic catalyst or honeycombed catalyst).
Paper at E.Tronconi and G.Groppi, comprise " Design of Novel monolith CatalystSupports For Gas/solid Reactions With Heat Exchange ", Chem.Eng.Sci.55 (2000), the structuring metal honeycomb-shaped catalyzer that has proposed use heat conduction among the 2161-2171 improves the method for being heated evenly property in the tubular reactor.The suggestion that these authors and other people model process discharge the self-contained thing of conductibility that designs has significantly reduced the gradient of catalyst temperature in the tubular reactor by the heat conduction of self-contained thing interconnected walls.But, relate to the temperature controlled problem of integral reactor and still exist.
A difficulty concerning any multi-tubular reactor device of being thought up to now is that reaction produces or needed heat must be provided or remove by tube wall by the heat exchange medium in the space that is between the pipe reactor.Therefore, catalyst overheating principal element is exactly the physical limitation of the internal heat transfer performance that occurs in these reactors in the exothermic reaction.Than the inner heat that produces of pipe reactor, this physical limitation (being typically expressed as the heat transfer coefficient of reactor or effective diameter to thermal conductivity) is usually too low, can not reach the required temperature of reactor control level of theoretical reactor efficiency that obtains.
There is other practical difficulty in monolithic catalyst itself used in multi-tubular reactor, especially relates to the problem of efficiently catalyst being filled and being installed to the commercial reactors pipeline.The shape of described pipe reactor and catalyst itself all is not desirable, therefore, has the slit between catalyst and the pipeline inevitably.Heat transmission resistance in the further augmenting response device of this slit meeting between catalyst and the heat-transfer fluid.Therefore, need to improve that monolithic catalyst is encapsulated into method in the pipe reactor, the heat transmission resistance minimum that a series of interfaces that exist between catalyst reactor and the heat-transfer fluid and material are produced.
Summary of the invention
The present invention relates to multi-tubular reactor, and monolithic catalyst is encapsulated into the highest method of radially heat transfer efficiency that makes self-contained pipe reactor interface in the pipeline of multi-tubular reactor in conjunction with monolithic catalyst.Directly solved whole heat transfer capacity adverse factors, for example comprised, the residual slit between monolithic catalyst and the pipe reactor these systems.
On the one hand, the present invention includes a kind of modified multi-tubular reactor that is used for the process fluid reactant.Described reactor comprises the reactor tube channel array that places cycling hot replacement fluids container that catalyst is housed, and the catalyst in the described reactor comprises at least a monolithic catalyst or catalyst support structures.Monolithic catalyst in preparation and the pipe laying, process fluid reactant under the temperature in being in design or predetermined technological temperature scope, above-mentioned scope depends on the concrete reaction that will carry out.
In order to satisfy the basic heat transfer requirement of these reactors, described monolithic catalyst or catalyst support structures will be made by Heat Conduction Material such as metal.Selected metal has known average thermal linear expansion coefficient, hereinafter, is sometimes referred to as first coefficient of expansion; And monolithic catalyst itself has enough thick wall and density of material, and the conductivity of heat of guaranteeing monolithic catalyst inside can not hinder under the temperature in the predetermined fluid range of work the heat conduction or spread out of reaction-ure fluid.
Described pipe reactor is also made by Heat Conduction Material such as metal, and described metal also has known thermal linear expansion coefficient, is sometimes referred to as second thermal coefficient of expansion hereinafter.Described pipe reactor also has wall thickness and density of material, can not hinder under the reactor operating temperature the heat conduction and spreads out of reaction-ure fluid with the thermal conductivity of guaranteeing described pipeline effectively.
At last, in these reactors, efficiently carry out the required stricter heat transfer requirement of the high heat release or the endothermic reaction in order to satisfy, select the size and the coefficient of expansion of monolithic catalyst section and reactor tube, reduce or eliminate slit between monolithic catalyst section and the pipe reactor basically, otherwise these slits may influence the heat transfer between catalyst section described in the reactor and the tube wall.In the present invention, the slit between described monolithic catalyst and the pipe reactor is called monolithic catalyst/pipe operations slit.The size of monolithic catalyst/pipe reactor system is depended in this slit, the thermal expansion character of monolithic catalyst and pipeline and the practical operation temperature of monolithic catalyst and pipeline in being installed to reactor and in actual the use.In order to satisfy heat transfer requirement of the present invention, under reactor that relates to selected technology and the used goal response device of catalyst operating condition, the slit between pipe reactor and monolithic catalyst or the catalyst support structures is reduced to is no more than about 250 microns value.
On the other hand, the present invention includes the method for assembling multi-tubular reactor, described reactor has self-contained section the reactor tube channel array that has wherein loaded one or more snippets monolithic catalyst or catalyst carrier.At first select the section of monolithic catalyst or catalyst support structures, make by Heat Conduction Material for described section, and have the design and the planning of highly-efficient processing fluid in above-mentioned technological temperature scope with first average thermal linear expansion coefficient.Also select the pipe reactor that forms by Heat Conduction Material with second average thermal linear expansion coefficient.
An aspect that is even more important selecting self-contained section and pipe reactor is to guarantee that described section and/or pipeline have suitable relative size.At first, determine the relative size of these parts, interfere coupling to make between self-contained section and the pipe reactor mutually noninterfere when mounted (interfering) or slidingtype effectively, like this when the temperature of temperature than described section of pipeline is high at least.Secondly, must set the relative size of described section and pipeline, guarantee when ducted section fluid that is full of under the temperature that is in the reactor processing temperature scope, the operation slit between described pipe reactor and described section is no more than about 250 microns.Bigger operation clearance distance can reduce the performance of reactor, and this is because heat transfer is poor.Preferred average clearance distance is zero or approaching zero.
At last, after the suitable size of determining these assemblies, self-contained section is inserted in the described pipeline.Relative size according to described assembly, inserting operation can be under the uniform temp at described section and pipeline and carry out, perhaps can be higher than under described section the condition and carry out, make to form between the described assembly not have and interfere or matching relationship that slidingtype is interfered in the temperature of described pipeline.
Can in pipeline, be provided for the mechanical device that keeps described self-contained section, especially so preferred when a plurality of catalyst section place same pipeline.But when in the reactor operating process, when fluid was flowed through pipeline in the technological temperature scope, the static friction between described section and the pipeline can increase, and this is enough for purpose of the present invention.As hereinafter describing more all sidedly, select to have self-contained section of visibly different average thermal linear expansion coefficient and pipe reactor and can guarantee to keep described section mode needed just by friction.
Description of drawings
Further illustrate the present invention with reference to the accompanying drawings, wherein:
Fig. 1 is the heat exchanger effectiveness and operation slit (Gap of various monolithic catalyst provided by the invention-pipe reactor combination
Op) graph of a relation;
Fig. 2 is the heat exchanger effectiveness and the effective function relation figure of gap size of monolithic catalyst device that places the axial placement of pipe reactor;
Fig. 3 has illustrated monolithic catalyst has been installed to equipment in the pipe reactor;
Fig. 4 has illustrated monolithic catalyst has been installed to another equipment in the pipe reactor;
Fig. 5 adds and understands monolithic catalyst is installed to another equipment in the pipe reactor.
Describe in detail
Single high heat-flux resistance in recognizing a series of low heat flux resistances will play the effect of heat " bottleneck ", when being limited in the heat output in the whole system thus, and the validity of improvement multi-tubular reactor efficient that the present invention may be better understood.In this case, the reduction of preceding a kind of resistance can not produce any remarkable influence to the hot-fluid that enters or leave reactor.In the multi-tubular reactor in conjunction with self-contained catalyst carrier of the metal of high conductance and reactor tube, internal heat flux resistance is very low usually, the resistance that the slit produced between monolithic catalyst and inner-walls of duct.The heat transmission resistance in this slit changes with its size and fluid content, but the resistance that common longshore current body has maximum to the path of reactor tube outer surface, when especially gap space is full of still air.
When handling the problem of gap space, can not ignore in these reactors other resistance to heat flux.Based on the reason of actual manufacturing, carrying, transportation and catalyst deposit, monolithic catalyst or catalyst carrier used in the multi-tubular reactor should be not oversize.Usually, can use a plurality of self-contained or section, they are shorter than the length of reactor tube, this is convenient to insert in the pipeline more easily, and takes out from pipeline, so that catalyst regeneration or replacement.
In order to ensure piling up in this reactor enough axial heat conduction is arranged between self-contained section, described section physics contact mutually, perhaps the intersegmental bridge joint element by high thermal conductance is in contact with one another.Can use spring or other device that produces pressure to keep contacting closely and good thermal conductivity between self-contained section in these stacking materials, but the measure that neither one is used to address this is that can improve self-contained section to the radially heat flux between the reactor tube walls.
Diameter of the present invention directly depends on to the control of heat flux operates slit (Gap between self-contained section and the reactor tube walls
Op) control.As mentioned above, the size in operation slit should not surpass 250 microns, and it directly depends in the system size, hot expansibility and the operating condition of self-contained section and reactor tube.More particularly, described operation slit Gap
OpBe defined as in this manual:
Gap
op＝Gap(T
0)-D×[CTE
2×(T
2-T
0)-CTE
1×(T
1-T
0)]
In the formula, Gap (T
0) be when being in room temperature T
0When (common 25 ℃), the gap between self-contained section OD and the pipeline ID, D is the average diameter of monolithic catalyst-reactor assembly, rounds half of dress section OD and pipeline ID sum; CTE
1And CTE
2It is monolithic catalyst and pipeline average thermal linear expansion coefficient separately; T
1And T
2Be respectively monolithic catalyst and reactor tube when all under reactor design operation condition, carrying out the interested reaction of institute, both partial operation temperature in monolithic catalyst that designs for high heat-flux and reactor tube length.When the diameter of described monolithic catalyst and/or reactor tube is to change or when irregular, can use the mean value of OD and ID in monolithic catalyst and reactor tube length.
Can confirm by the experiment in slit between monolithic catalyst-reactor tube of measuring different sizes for controlling the importance that heat flux radially controls the slit.Described measurement is that conductibility is arrived reactor for self-contained section, perhaps measures to the hot-fluid of heat-exchange tube on every side, and described reactor or heat-exchange tube remain under the constant temperature by the heat-exchange fluid of pipe outer circulation.
In a useful experimental rig, the cellular self-contained section steel reactor tube that places long 30cm of the cylindrical metal of diameter 2.85cm, length 25cm, the cold water that its continuous on every side circulation is 20 ℃, force hot-air to pass through self-contained section, amass and temperature drop with quality-flow controller and thermocouple measurement air fluid at self-contained section entrance and exit end.Use geometry, air inlet and outlet temperature, water temperature and the MAF data of heat-exchange tube, can pass through following equation calculated population heat transfer efficiency h
Eff:
h
Eff=ρ C
pΦ
G/ L (ln (T
Advance-T
Water)/(T
Go out-T
Water))
In the formula, ρ is the density of gas under standard temperature and pressure (STP), C
pBe The Thermal Capacity of Gaseous, Φ
GBe the volume flow rate of gas under standard temperature and pressure (STP), L is the length of monolithic catalyst test section.
When carrying out this test, in the whole length of heat-exchange tube, keep 20 ℃ thermal boundary condition very important.Therefore, it is enough high that the flow velocity of water is wanted, so that the difference of water inlet and outlet temperature remains below 0.1 ℃, the flow velocity that perhaps is more preferably by improving water can not increase the exchange rate of measurement.
The gas flow rate that is suitable for the pilot system of this geometric configuration is 0.5-20.7kg/s/m
2Though the radially heat transfer in self-contained section of the metal is mainly undertaken by the wall conduction, and irrelevant with gas flow rate to a great extent.But the test under the high gas flow rate high Peclet number of high convection current/conduction transport ratio technology (perhaps corresponding to) helps to make impacting shaft to conductibility and gas-solid heat transfer limitations minimum.
The heat transfer efficiency data that observe in above-mentioned test are listed in the table below in 1.The flox condition that is suitable for producing the heated gas of this data is included in flowing nitrogen and the 17kg/s/m under 200-400 ℃
2Flow velocity.The copper of surveying (Cu) extrude copper by high conductance usually for self-contained section and form for self-contained section, as described in laid-open U.S. Patents application No.US-2003-0100448-A1, all self-contained section smooth layer that is supporting the whole copper pipe that applies.The diameter of the square duct of described copper monolithic catalyst is 0.92mm.
Chang Yong aluminium (Al) is made by aluminium block for self-contained section in these trials, and has the circular channel of 1.52mm channel diameter.The self-contained segment length 25mm of described aluminium, and, be mounted to the passage that is arranged in rows for testing, length overall is 250mm.
The relative value of heat exchanger effectiveness shown in the table 1 is corresponding to the increment percentage of heat transfer efficiency in " substantially " system, described fundamental system is made up of for self-contained section copper, and its size can make under the room temperature mounting condition and stay about 500 microns slit between the smooth self-contained section outer surface and heat-exchange tube smooth inner wall.The data of described " substantially " system are to produce under 200 ℃ the condition at the inlet nitrogen temperature of heating usually.
The self-contained material (as shown in table 1) that uses two different nitrogen temperatures and two to have the different coefficients of expansion and different geometric configurations helps to illustrate the relation of influencing each other of geometric configuration and thermal expansion, for the overall efficient encapsulation that obtains to be used to conduct heat, this point must be considered.In order to determine the size in operation slit, promptly the size in slit (being the relevant parameter of metering system heat transfer property) under operating condition is used the logarithmic mean temperature based on gas feed and outlet temperature and conduit temperature.
Δ T
Log is average=(T
Air inlet-T
Exit gas)/ln (T
Air inlet-T
Pipe)/(T
Give vent to anger-T
Pipe)
This mode is supposed to keep balance between gas and the solid temperature.
In the table 1 data of listed gap size be initial or room temperature under pipe/self-contained section gap size (in micron).In these embodiments, described operation slit (Gap
Op) size all is lower than the gas slit (T that writes down under the room temperature in all cases slightly
0), this is because the relatively hot coefficient of expansion of steel, copper and aluminium and self-contained section the gas temperature height of flowing through.
The relative heat transfer efficiency of table 1-
| Metal | Cu | Cu | Al |
| N 2Temperature | 200 | 400 | 400℃ |
| Initial slit (T 0) | |||
| 64μm | 278％ | 343％ | 361％ |
| 127μm | 198％ | 253％ | 318％ |
| 178μm | 154％ | 203％ | |
| 254μm | 133％ | 174％ | 209％ |
| 508μm | 100％ * | 117％ | 126％ |
* base case
As above the data of table 1 are clear shows that gap size reduces the exchange rate that directly influences in the multi-tubular reactor with monolithic catalyst.The fact that the influence that the slit reduces will change with the composition and the configuration of system also is conspicuous.
Fig. 1 is heat exchanger effectiveness figure, shows between relative heat transfer percentage RHT (%) and self-contained section and the tube wall to operate slit (Gap
Op) size (in micron) graph of a relation under the condition that is similar to the described data of generation table 1.Described relative heat transfer (RHT) value plots and surpasses 500 microns down basic percentages that conduct heat in operation slit, operation slit Gap
OpIn micron.Data representation shown in Figure 1 a series of three kinds of test configurations, be similar to shown in the table 1 those, be included in the test of self-contained section of self-contained section of two copper under the temperature and the aluminium under a temperature.Action required slit below 250 microns is represented by arrow, operates the slit parameters calculated and insert value representation influence on self-contained-pipe operation slit schematic diagram.
Fig. 1 is clear to have confirmed that under operating condition gap size directly controlled the heat flux of all configurations of being tested, does not consider the concrete self-contained configuration tested, and heat transfer efficiency significantly improves under the situation of roughly the same gap size.Therefore, according to the character of material and the temperature of operating environment, by the heat transfer property of selecting suitable self-contained OD and the initial physical dimension of managing ID to obtain almost to want arbitrarily.Certainly, under assembling condition, the thermal expansion of described structural material and the size in slit can apply physical constraints to accessible operation gap size in many cases, no matter be in room temperature or under other temperature.
Based on as table 1 and data shown in Figure 1, about operation slit more than 250 microns obviously can significantly reduce heat exchanger effectiveness, and therefore reactor can not provide significant heat flux advantage (than the reactor of current use pellet type catalyst).Therefore, gap size should keep being no more than threshold values usually.
Certainly, the size in the operation slit between self-contained section and the pipe can change with self-contained section circumference, so that reaches the degree that self-contained section circumference character can not accurately cooperate described pipe.The little variation of gap size normally allows, but big not controlled slit change (for example, cause the surface roughness on self-contained section surface and the inner surface of pipe excessive) can the appreciable impact hot-fluid, this will be avoided usually.
On the other hand, the controlled change of operation gap size can be as the mode of controlling reaction temperature in the reactor operating condition better.The variation of these gap size can be radially, promptly relates to groove or other variation at self-contained section appearance, controls self-contained section circular order thus; Perhaps, they can be axial, relate to self-contained section continuous in groove on the circumference or the stacking material, and its outside size and/or shape difference are to change the operation slit of each section.
For the degree that can control heat flux by the controlled change of self-contained section appearance of conductibility is described, a cover aluminium has axial notch along its circumference by machining formation for self-contained section and changes on self-contained section surface.Gained curve (shown in the interior illustration I among Fig. 2) is represented by self-contained section M that usually described self-contained section M has two different pipe-contacts or pipe-approximated position A
1And A
2, represent the different gap size (G among the single reactor tube T separately
1And G
2).
Data among Fig. 2 are at self-contained-pipe combination, and wherein, the surface portion A2 with groove forms self-contained-pipe seam crack size of 500 microns, and it is 125mm that surface portion A1 remaining or that do not have groove makes self-contained-pipe seam crack.Described data show heat transfer efficiency linear change between two limiting values of gap size of self-contained section, maximum when average gap size is 125 microns (not having surface groove), minimum when forming 500 micron gap on self-contained section whole surface through machining.Significantly, even when the self-contained section circumference of half stays 500 micron gap size,, still can reach the heat transfer efficiency of the baseline value 150% that surpasses 500 micron gap if self-contained section remaining circumference forms 125 microns slit.
Well contact between these self-contained section of data demonstrations and the pipeline, and by the importance of design slit control acquisition to heat flux control.The heat flux of using the slit to control to control to reactor tube especially simple and easily method be in single pipeline, to use self-contained section stacking material of various outer diameter.This method provides higher heat flux on the flow path of some reactants by pipeline, lower heat flux is provided on the flow path of other parts.Use two, self-contained section of three or more various outer diameters can relatively accurately control reactor by the heat flux on the whole flow path of multi-tubular reactor.
As mentioned above, the generally acknowledged characteristic that is beneficial to the ceramic particle catalyst carrier that is used in the multi-tubular reactor at present is to form hot spot easily on the length of reactor tube in catalyst bed.These hot spots have reduced the selectivity of reactor, have also produced safety problem.
Addressing these problems does not need all fully beaded catalyst to be replaced to monolithic catalyst in each case.A kind of useful method is that heat conduction monolithic catalyst or catalyst carrier such as honeycomb metal thing are positioned at selected position on the length of this reactor tube, and it must control the temperature of process fluid on this position.The described self-contained section high-termal conductivity along its axis of flow (common direction orientation along the axle that is parallel to reactor tube and those pipes of fluid process) helps to reduce axial thermograde in the pipeline.Then, control self-contained section-reactor tube slit and regulate the heat flux that enters or leave reaction-ure fluid by reactor tube outer wall and heat-exchange fluid, this permission any desired location in the beaded catalyst bed is removed heat or is increased heat the process fluid that will react.
Be suitable for producing self-contained section manufacturing technology involucrum honeycomb metal thing expressing technique and sheet metal winding process at present as self-contained section honeycomb metal thing.Any in these two kinds of methods can both factory length be that 1-100cm, diameter are self-contained section of 2-15cm.Have the section that is in interior length of these scopes and diameter is suitable for in the present invention very much.
Being applied to the self-contained section catalyst material of going up the required chemical reaction of promotion can be applied on the surface of self-contained section of metal by coating form as a rule.This active catalyst is applied to mutually can uses the known standard method of those skilled in the art to carry out on the metal surface, for example in the exhaust-gas treatment of automobile and other application, various metal oxides are applied on the honeycomb metal thing, wherein, hydro carbons is by catalytic oxidation.Apply catalyst and normally before inserting reactor tube, carry out, also be feasible though carry out catalyst processing afterwards, and be useful in some cases self-contained section.
Described active phase material depends on described application, and in most cases can be identical, perhaps the material of at present used random packing is done a little modification.Typical catalyst material comprises metal, as Pt, Pd, Ag, Au, Rh, Re, Ni, Co, Fe, V, Ti, Cu, Al, Cr etc. and their oxide, chloride, sulfide etc., and their mixture.In some cases, described metal itself can have catalytic activity for self-contained section.In other cases, modification can be carried out before use in the surface that described metal is self-contained section, for example, carries out oxidation or chlorination.Also can (comprise) form and the structure that changes self-contained section surface, be used on self-contained section wall, forming or change porosity, form the aperture and the pore-size distribution of OK range.
Can use many diverse ways to fill self-contained section in the pipeline of multi-tubular reactor, described self-contained section size can make average gap size be in the limited range of allowing.For the application of process fluid at high temperature, can carry out easily by selecting to have self-contained section of the thermal coefficient of expansion higher that pipeline is filled and the slit is controlled than the coefficient of expansion of reactor tube.Utilize this selection reference, described pipeline and self-contained section can have following size: be in selected self-contained section described pipe and self-contained section temperature following time is installed, make and stay little slit (non-interference coupling) between the two.
Afterwards, when high temperature fluid processing began in operant response device environment, the temperature rising of self-contained section and pipeline can cause self-contained section expansion greater than the expansion of reactor tube.This will reduce or eliminate the small gap between self-contained section surface and the reactor tube inwall, and guarantee good approaching or heat conduction contact between them.
Perhaps, for being designed for the reactor that carries out exothermic reaction during self-contained section temperature is lower than pipe temperature, thermal dilation difference is useful to make self-contained section of pipeline shrinkage ratio shrink faster.In any case, when reactor was closed, reactor returns in the process of room temperature can recover initial slit usually, helped to take out and/or replace self-contained section.
Provide the pipeline of just self-contained section-thermal expansion of pipeline difference and self-contained segment structure examples of material to be included in and install self-contained section that forms by aluminium or copper in the pipe reactor of forming by nickel or steel.The average thermal linear expansion coefficient that copper and aluminium are self-contained section is respectively 20.2 * 10 in 25-500 ℃ temperature range
-6/ ℃ and 27.4 * 10
-6/ ℃, and stainless swell value is 15-19 * 10
-6/ ℃, the swell value of carbon steel is 10 * 10
-6/ ℃.
When the reactor application needs to use the material (being convenient to install) that does not have thermal expansion difference as mentioned above, can use any installation procedure.A kind of program depends on the following fact: the thermal coefficient of expansion that is used for the candidate material of pipe reactor structure is positive, and promptly described material expands when heating.By this fact, the size that correctly is identified for self-contained section of reactor assemblies and pipeline comprises and heats described pipeline when mounted, and/or cools off described self-contained section, forms essential not interference or slidingtype is interfered coupling between these elements.Afterwards, the thermal expansion of the cooling of pipeline and contraction and/or self-contained section can be securely fixed in the described pipe described self-contained section.
Based on the expansion characteristics of described material and to the control of the initial size of described parts, accurately adjust the size of described self-contained section and tube elements, guarantee to keep required little average gap size between the two or do not have the slit when described self-contained period operating temperature following time that all is in described reactor with pipeline.For example, make cooling fluid cycle through self-contained section, make fluid circulation around the reactor tube of heat simultaneously, between described pipeline and self-contained section, form temporary transient slit once more, be convenient to after reactor is closed, to remove self-contained section of installation like this.
In some cases, adjust the size of self-contained section and pipeline in installation process, it is not practicable forming or keeping little the slit, and to exist slidingtype to interfere the pipeline load of coupling between described pipe and self-contained section be necessary.Slidingtype interferes coupling to be meant contact coupling between self-contained section and the pipeline, make self-contained section tighter or slightly loose ground be installed in the pipe hole, by applying the axial installation active force that is lower than self-contained section or pipe reactor end-terminal compressive strength, described self-contained section can be forced to descend in the hole.
Can use many with self-contained section method that is installed in the reactor pore (size is fit to interfere coupling).Slightly and only need light the pressure just can install the time when interfering, can shift onto on the position in the heat-exchange tube by inertia for described self-contained section.Illustrated among Fig. 2 and carried out the inertia installed device.A pair of traction wheel 10 on same level (separate in the slit 12 that is slightly smaller than self-contained section 14 diameter) rotation at a high speed in opposite direction.Then, self-contained section 14 adds in the slit 12, and pushes the hole 16 of reactor tube 18 to.If need, the obstacle (not shown) is provided in described hole, control the described section final position in pipe.
Fig. 3 and 4 has illustrated the Pneumatic method that self-contained section is installed or be expressed in the reactor tube.In Fig. 3, air collector 20 provides downward driving force to piston rod 22, and described piston rod is connected to and is positioned on self-contained section 14 planar piston 24 on the end.Promoting air collector 20 rapidly can and enter in the hole 16 of reactor tube 18 section 14 emissions, perhaps can described section be pressed in the described hole by slow promotion.
In Fig. 4, reactor tube 18 plays the effect of the outer rim perisporium of pressure measuring cylinder, and piston sheet 24a places self-contained section 14 top (being driven into hole 16).The size of described piston sheet can provide reactor tube walls sealing closely, and air pressure is applied to the top of piston sheet, forces self-contained section to enter in the described pipeline downwards.Device (not shown) as metal wire or chain can be connected on the piston sheet, and it is pulled out from pore.Shown in Fig. 3 and 4, also can the pneumatic step of reverse enforcement, self-contained section is taken out from reactor tube.
As mentioned above, between selected self-contained section and reactor tube, provide good shape uniformity, and form on the inner surface of self-contained section outside and reactor tube rationally that smooth surface is to guarantee the key factor in the efficient heat transfer required slit control in the multi-tubular reactor.At present, not all be suitable for forming as the manufacture method of self-contained section of the metal of multi-tubular reactor catalyst carrier can make self-contained section with smooth surface.For example, extrusion method just has remarkable advantages, and it can make cellular self-contained section that wall thickness is big, conductibility is high efficiently, in some cases, produces the cellular thing that does not have epidermis or have epidermis, and described epidermis can not form smooth periphery.
Making this self-contained section the method for optimizing that is used for multi-tubular reactor comprises in the described self-contained section metal shell pipe that inserts smooth surface.By using conventional extruding-cooperation or heat-contraction technology, this method can provide the self-contained compound of being made up of the cellular core in the metal shell pipe, and it presents the same inner as far as possible efficiently (core-shell) conductivity of heat with the cellular self-contained intersegmental part conductibility with integrated epidermis.Use other advantage of this metal shell to comprise this shell of easy manufacturing, make it to have high-termal conductivity, good outside dimension permission and high-caliber smooth outer surface degree.
From as can be known above, the present invention can be used in various chemistry and petrochemical reactions and the reactor, and for safety with operate described reactor assembly economically, it is very crucial radially conducting heat.This will comprise any reaction of carrying out at present in multi-tubular reactor, described reactor has the relatively little pipeline array of diameter that is immersed in the external heat exchange medium.The object lesson of this reaction comprises that the hydro carbons partial oxygen changes into as products such as oxirane, formaldehyde, phthalic anhydride, maleic anhydride, methyl alcohol.Other example comprises oxychlorination process, forms as dichloroethylene; Hydrocarbon steam is restructured as product synthesis gas (CO+H
2); And the Fischer-Tropsch synthetic method that synthesis gas is changed into liquid hydrocarbon.Certainly, whether temperature controlled reaction is carried out above the solid catalyst of multi-tubular reactor no matter other benefits from improvement, and they also can be benefited in these self-contained reactors.
In brief, the security that obvious narrower temperature range (this can not effectively realize in popular response device technology) will improve these technologies in the reactor operation of the present invention, prolong the service life of catalyst, and improve process choice required reaction and product.In addition, the present invention can make described reactor operate under the higher reaction heat load to carry out, obtain output higher under time per unit and the volume thus, significantly reduces pressure simultaneously and falls.Back one advantage has reduced the load of pump and compressor, has reduced the running cost and the capital cost of reactor, is equating or is hanging down and use higher cycling rate under the compression demand, and described reactor is more being operated under the constant compression force level.At last, be highly to repeat owing in reactor tube, pile up self-contained section, so simplified classification, load and the design of catalyst reactor with simple.
More than explanation concrete to the present invention and preferred implementation only limit to illustrative purposes, be used to anything but limit.Clearly, in the scope of accessory claim book, for concrete purpose can be carried out various modifications to those specific embodiment.
Claims (11)
1. one kind is used for the multi-tubular reactor that fluid is processed, and it comprises the reactor tube channel array of the catalyst filling that places cycling hot replacement fluids container,
Wherein, the catalyst in the described reactor comprises at least a monolithic catalyst or catalyst support structures; Process fluid reactant under the temperature in being in predetermined technological temperature scope, described self-contained structure is formed by Heat Conduction Material, and has first average thermal linear expansion coefficient;
Described reactor tube is formed by the Heat Conduction Material with second average thermal linear expansion coefficient; With
In following time of temperature in described fluid remains on the technological temperature scope, the operation clearance distance between described reactor tube and monolithic catalyst or the catalyst support structures is no more than 250 microns.
2. multi-tubular reactor as claimed in claim 1 is characterized in that, described operation clearance distance is by following formula calculated distance Gap
Op:
Gap
op＝Gap(T
0)-D×[CTE
2×(T
2-T
0)-CTE
1×(T
1-T
0)]
In the formula, Gap (T
0) be to be in the external diameter OD of room temperature monolithic catalyst of following time or catalyst support structures and the gap between the pipe reactor inner diameter, ID when both, D is half of external diameter OD and inner diameter, ID sum; CTE
1And CTE
2It is monolithic catalyst or catalyst support structures and pipe reactor average thermal linear expansion coefficient separately; T
1And T
2It is respectively the operating temperature of monolithic catalyst or catalyst support structures and reactor tube.
3. multi-tubular reactor as claimed in claim 1 is characterized in that, described reactor tube comprises a plurality of pipeline terminal monolithic catalyst or catalyst support structures to the mutual thermo-contact of end of placing.
4. multi-tubular reactor as claimed in claim 2 is characterized in that, the operation clearance distance between described reactor tube and monolithic catalyst or the catalyst support structures is along the length variations of reactor tube.
5. multi-tubular reactor as claimed in claim 2 is characterized in that, the operation clearance distance between described reactor tube and monolithic catalyst or the catalyst support structures is along the circumferential variation of reactor tube.
6. multi-tubular reactor as claimed in claim 1 is characterized in that, described first average thermal linear expansion coefficient is greater than second average thermal linear expansion coefficient.
7. an assembling is used for the method for the multi-tubular reactor of process fluid in the technological temperature scope, and described reactor has self-contained section the reactor tube channel array that wherein loads one or more snippets monolithic catalyst or catalyst carrier, and described method comprises the steps
Select monolithic catalyst or catalyst support structures self-contained section, make by Heat Conduction Material for described section with first average thermal linear expansion coefficient;
The pipe reactor that selection is formed by the Heat Conduction Material with second average thermal linear expansion coefficient;
Adjust the size of self-contained section and/or reactor tube, (i) temperature following time is installed, between self-contained section and reactor tube, form and do not interfere or slidingtype is interfered coupling when being in selected self-contained section; When (ii) being full of self-contained section with fluid under the temperature in being in the technological temperature scope, the average clearance distance between described reactor tube and the section is no more than about 250 microns; With
Described section is inserted in the reactor tube.
8. method as claimed in claim 7 is characterized in that, described self-contained section size can form non-interference coupling with reactor tube effectively, and described first average thermal linear expansion coefficient is greater than second average thermal linear expansion coefficient.
9. method as claimed in claim 7, it is characterized in that, the size of adjusting self-contained section and/or reactor tube relates to one or two heating in self-contained section and the reactor tube and/or is cooled to selected installation temperature, forms not interfere or slide and interfere coupling between them.
10. method as claimed in claim 7 is characterized in that, described monolithic catalyst or catalyst carrier are the compounds that comprises cellular core parts and metal casing element.
11. method as claimed in claim 7 is characterized in that, described self-contained section size can form slidingtype with reactor tube effectively and interfere coupling, and described section by applying in inertia or the pneumatic action power insertion reactor tube.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/750,472 | 2003-12-31 | ||
| US10/750,472 US20050142049A1 (en) | 2003-12-31 | 2003-12-31 | Multi-tubular reactors with monolithic catalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1901988A true CN1901988A (en) | 2007-01-24 |
| CN100464831C CN100464831C (en) | 2009-03-04 |
Family
ID=34701203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800391300A Expired - Fee Related CN100464831C (en) | 2003-12-31 | 2004-12-15 | Multi-tubular reactors with monolithic catalysts |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US20050142049A1 (en) |
| EP (1) | EP1699552A4 (en) |
| CN (1) | CN100464831C (en) |
| WO (1) | WO2005065187A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844109A (en) * | 2011-04-04 | 2012-12-26 | 戴维加工技术有限公司 | Monolithic reactor |
| CN102985195A (en) * | 2010-06-08 | 2013-03-20 | 三照普燃料公司 | Various methods and apparatuses for an ultra-high heat flux chemical reactor |
| CN109647290A (en) * | 2018-12-10 | 2019-04-19 | 浙江工业大学 | Nanometer titanium dioxide is violent/alumina composite coating tubular reactor and its preparation method and application |
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| WO2006082933A1 (en) * | 2005-02-04 | 2006-08-10 | Ngk Insulators, Ltd. | Reactor of selective-permeation membrane type |
| US7906079B2 (en) * | 2006-12-14 | 2011-03-15 | Catacel Corp. | Stackable structural reactor |
| IT1394068B1 (en) * | 2009-05-13 | 2012-05-25 | Milano Politecnico | REACTOR FOR EXOTHERMIC OR ENDOTHERMAL CATALYTIC REACTIONS |
| US8814961B2 (en) | 2009-06-09 | 2014-08-26 | Sundrop Fuels, Inc. | Various methods and apparatuses for a radiant-heat driven chemical reactor |
| US8771387B2 (en) * | 2009-06-09 | 2014-07-08 | Sundrop Fuels, Inc. | Systems and methods for solar-thermal gasification of biomass |
| US9663363B2 (en) | 2009-06-09 | 2017-05-30 | Sundrop Fuels, Inc. | Various methods and apparatuses for multi-stage synthesis gas generation |
| US9295961B2 (en) | 2012-03-26 | 2016-03-29 | Sundrop Fuels, Inc. | Various methods and apparatuses for internally heated radiant tubes in a chemical reactor |
| ITMI20122251A1 (en) * | 2012-12-28 | 2014-06-29 | Eni Spa | MULTI-TEXTURED REACTOR FOR CHEMICAL PROCESSES WITH HIGH HEAT EXCHANGE |
| ITMI20131439A1 (en) | 2013-09-03 | 2015-03-04 | Eni Spa | BED TUBULAR REACTOR, PACKED FOR EXOTHERMIC OR ENDOTHERMAL CATHALTIC REACTIONS |
| US9627699B2 (en) | 2013-11-06 | 2017-04-18 | Watt Fuel Cell Corp. | Gaseous fuel CPOX reformers and methods of CPOX reforming |
| US9624104B2 (en) | 2013-11-06 | 2017-04-18 | Watt Fuel Cell Corp. | Liquid fuel CPOX reformers and methods of CPOX reforming |
| CN105705227B (en) | 2013-11-06 | 2018-09-25 | 瓦特燃料电池公司 | Liquid fuel CPOX reformer and fuel cell system and the method for generating electric power |
| AU2014346844B2 (en) | 2013-11-06 | 2017-06-15 | Watt Fuel Cell Corp. | Chemical reactor with manifold for management of a flow of gaseous reaction medium thereto |
| MX2016004622A (en) | 2013-11-06 | 2016-08-01 | WATT Fuel Cell Corp | Integrated gaseous fuel cpox reformer and fuel cell systems, and methods of producing electricity. |
| US10676354B2 (en) | 2013-11-06 | 2020-06-09 | Watt Fuel Cell Corp. | Reformer with perovskite as structural component thereof |
| GB201403787D0 (en) | 2014-03-04 | 2014-04-16 | Johnson Matthey Plc | Steam reforming |
| AU2021295431A1 (en) * | 2020-06-26 | 2022-11-24 | Topsoe A/S | A structured catalyst |
| GB202015180D0 (en) * | 2020-09-25 | 2020-11-11 | Johnson Matthey Davy Technologies Ltd | Methods and apparatus for installation and removal of catalyst carriers |
| GB202202226D0 (en) * | 2022-02-18 | 2022-04-06 | Johnson Matthey Davy Technologies Ltd | Apparatus and methods for installation and removal of catalyst carriers |
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| DE3521767A1 (en) * | 1985-06-19 | 1987-01-02 | Basf Ag | CATALYST FIXED BED ASSEMBLY USING HONEYCOMB-BODY |
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- 2003-12-31 US US10/750,472 patent/US20050142049A1/en not_active Abandoned
-
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- 2004-12-15 CN CNB2004800391300A patent/CN100464831C/en not_active Expired - Fee Related
- 2004-12-15 EP EP04814307A patent/EP1699552A4/en not_active Withdrawn
- 2004-12-15 WO PCT/US2004/042106 patent/WO2005065187A2/en not_active Application Discontinuation
-
2009
- 2009-03-16 US US12/404,531 patent/US8354083B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102985195A (en) * | 2010-06-08 | 2013-03-20 | 三照普燃料公司 | Various methods and apparatuses for an ultra-high heat flux chemical reactor |
| CN102844109A (en) * | 2011-04-04 | 2012-12-26 | 戴维加工技术有限公司 | Monolithic reactor |
| CN102844109B (en) * | 2011-04-04 | 2015-03-25 | 戴维加工技术有限公司 | Monolithic reactor |
| CN109647290A (en) * | 2018-12-10 | 2019-04-19 | 浙江工业大学 | Nanometer titanium dioxide is violent/alumina composite coating tubular reactor and its preparation method and application |
| CN109647290B (en) * | 2018-12-10 | 2021-08-24 | 浙江工业大学 | Nano manganese dioxide/aluminum oxide composite coating tubular reactor and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050142049A1 (en) | 2005-06-30 |
| EP1699552A2 (en) | 2006-09-13 |
| WO2005065187A2 (en) | 2005-07-21 |
| WO2005065187A3 (en) | 2006-01-05 |
| CN100464831C (en) | 2009-03-04 |
| US20090176895A1 (en) | 2009-07-09 |
| US8354083B2 (en) | 2013-01-15 |
| EP1699552A4 (en) | 2008-01-16 |
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